JPH0345092B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to linear aromatic polyesters consisting of bisphenol and dicarboxylic acid monomer residues, the carboxylic acid end groups of which have been structurally modified to provide a product with increased stability against hydrolysis. . More particularly, the present invention includes dicarboxylic acid ester end groups derived from certain monofunctional fluorine-substituted aliphatic alcohols, i.e.
It relates to such polyesters containing fluoroalkyl oxycarbonyl ester terminal substituents. Linear aromatic polyesters made from aromatic dicarboxylic acids and bisphenols are well known as they are suitable for applications such as molding, extrusion, casting and film forming. For example, U.S. Pat.
No. 3216970 describes a linear aromatic compound consisting of monomer residues of isophthalic acid, terphthalic acid, and bisphenolic compounds produced by a polyesterification reaction of bisphenols (including biphenols) and acyl halides of terephthalic acid and isophthalic acid. The production of family polyesters is disclosed. Such polymeric compositions are known to be useful in the production of various films and fabrics. Furthermore, when formed into useful articles by conventional techniques, these compositions provide properties superior to articles formed from other linear polyester compositions. For example, aromatic polyesters are known to have various useful properties such as good tensile strength, impact strength and flexural strength, high heat distortion and pyrolysis temperatures, resistance to ultraviolet radiation and good electrical properties. There is. Aromatic polyesters particularly suitable for molding may also be prepared by reacting organic diacid halides with difunctional aliphatic reactive modifiers such as glycols and subsequently reacting this product with bisphenol compounds. The resulting polyester has a reduced melt viscosity and melting point, which means that it can be used at temperatures within the operating limits of conventional forming equipment (i.e., temperatures below about 300°C and pressures of about 2000 psi (about 1400 kg/cm ² )). ) to facilitate molding. Glycol modified polyesters of this type are fully disclosed in US Pat. No. 3,471,441. In order to produce superior molding resins on a commercial scale, polymers must be able to be conveniently molded without significant deterioration of their physical properties.
In this regard, although the aromatic polyesters mentioned above generally exhibit excellent physical and chemical properties, a persistent and troublesome problem is their susceptibility to hydrolytic degradation at elevated temperatures. This sensitivity to the combined effects of heat and moisture is also demonstrated in commercially available polycarbonate resins, as evidenced by the desirability of reducing the resin's moisture content to below about 0.05% prior to molding. . However, aromatic polyester resins often degrade more rapidly than polycarbonate resins and exhibit a marked tendency to become brittle. This is demonstrated by the loss of tensile strength that can occur when aromatic polyester resins are molded and subsequently immersed in boiling water. In order to increase the stability against hydrolysis of a linear aromatic polyester consisting of bisphenol and a dicarboxylic acid monomer residue, the production of polyester from this bisphenol and a dicarboxylic acid diacyl halide reactant is performed using p-tertiary butylphenol. It can be carried out in the presence of a phenolic compound with a monohydroxyl group such as (according to Japanese Patent Application Laid-open No. 53-8696)
Proposed. The monofunctional phenolic compound reacts with the terminal carbonyl halide substituent in the polyester to form a carboxylic acid ester end group derived from the monofunctional phenolic reactant. However, modifications such as the introduction of terminal carboxylic ester groups derived from monofunctional phenols (e.g. p-tertiary butylphenol) into this polyester, as exemplified by the data in the table below, can reduce the does not increase its hydrolytic stability enough to make it commercially attractive. Japanese Patent Application No. 55-753725 (Japanese Unexamined Patent Publication No. 56-8429 filed on the same day as the present application) contains a carboxylate end group derived from a monofunctional hydrocarbon alcohol having 8 to 45 carbon atoms; A linear aromatic polyester consisting of bisphenol and dicarboxylic acid monomer residues having improved hydrolytic stability is disclosed. 1982-
No. 8430) discloses an improved method for producing such polyesters by transesterification polymerization. The main object of the present invention is to substantially retain the other beneficial physical and chemical properties of this polyester;
The object of the present invention is to provide a linear aromatic polyester with increased stability against hydrolysis. The present invention is directed to a linear aromatic polyester consisting of monomer residues of bisphenol and an aromatic dicarboxylic acid, the terminal residues of the polyester chain consisting of residues of the dicarboxylic acid; The terminal carboxylate group of the terminal dicarboxylic acid residue consists of a carboxylic acid ester substituent derived from a fluorine-substituted aliphatic monofunctional alcohol having 1 to 45 carbon atoms.
The proportion of the fluorine-substituted aliphatic alcohol-derived ester substitution, etc. is at least about 5 mole percent based on the total number of moles of end groups in the polyester. The present invention is also directed to improving the process for producing this polyester by the polymerization esterification reaction of the bisphenol and the diacyl halide of the dicarboxylic acid. This improvement involves the reaction of about 0.1 to 50 mole percent or less of a fluorine-substituted monofunctional aliphatic alcohol with its diacyl halide (e.g., diacyl chloride or bromide) prior to or simultaneously with the polymerization reaction. It consists in making the proportion of fluorine-substituted alcohol dependent on the number of moles of the diacyl halide used in the reaction. This improved polyester of the invention is a carboxylic acid derived from the corresponding unmodified polyester and other monofunctional hydroxy compounds, such as p-tertiary butylphenol (as shown by comparison of the data in the table below). It is characterized by increased hydrolytic stability compared to the corresponding polyester with ester end groups. This polyester of the present invention has the beneficial chemical properties of conventional bisphenol-dicarboxylic acid linear aromatic polyesters.
Possesses substantial physical properties. It is known to produce linear aromatic polyesters consisting of bisphenol and carboxylic acid monomer residues containing terminal hydroxyl groups and/or terminal carboxylate groups. The terminal carboxylate group is −
COOH groups and their derivatives, such as carboxylate end groups (such as -COONa), carbonyl halide end groups (such as -COCl), and carboxylic acid ester end groups [e.g. (the disclosure of which is hereby incorporated by reference)
esters of monohydroxyl organic compounds such as butylphenoloxycarbonyl ester end groups]. The polyesters of this invention are structurally characterized by terminal carboxylate groups consisting of carboxylic acid ester groups derived from fluorine-substituted monofunctional aliphatic alcohols having from 1 to 45 carbon atoms. This fluorine-substituted ester end group of the polyester of the invention corresponds to the general formula -COOR, where R represents the organic residue of the monofunctional fluorine-substituted aliphatic alcohol. This fluorine-substituted aliphatic residue in the terminal carboxylic ester group of the polyesters of the invention is generally saturated and therefore does not contain ethylenic or acetylenic unsaturation. This fluorine-substituted residue of the terminal ester group contains, in addition to the fluorine substituent, aromatic substituents such as phenyl substituents, aliphatic ether substituents, and other halogen substituents (e.g., chlorine or bromine). However, it does not contain substituents such as hydroxyl groups that can undergo esterification in the polymerization esterification reaction used in the production of the polyester of the present invention. Preferably, this fluorine-substituted radial contains or has only a carbon-fluorine bond in addition to a carbon-carbon bond, i.e., only a fluorine substituent.
Contains only fluorine and carbon-hydrogen bonds, ie only fluorine and hydrogen substituents. The fluorine-substituted radical of the terminal carboxylic acid ester group may be cyclic, but is preferably an acyclic aliphatic residue. If acyclic, the fluorine substituent can be a straight or branched alkyl group. Preferably, the fluorine substituents of the terminal carboxylic acid ester substituents of the polyesters of the present invention are straight chain aliphatic residues. The fluorine-substituted radical of this terminal ester group of the polyester of the invention is preferably a primary, secondary, or tertiary fluorine-substituted aliphatic alcohol containing one or more fluorine substituents, i.e. Can be derived from dilated alcohols. Preferably the fluorine-substituted radical is derived from a primary fluorine-substituted aliphatic alcohol. The number of fluorine-substituted aliphatic residues in the terminal carboxylic acid group of the polyester of the present invention is 1 to 45, preferably 3 to 20.
Contains 5 carbon atoms. Particularly preferred fluorine-substituted aliphatic groups according to the invention contain 10 to 20 carbon atoms. The fluorine-substituted radicals of the terminal ester groups of the polyesters of the present invention are exemplified by the following corresponding representative monofunctional fluorine-substituted aliphatic alcohols from which they are derived: CH ₂ FOH CF ₃ CH ₂ OH CHF ₂ CH ₂ OH CF ₃ CH(OH)CHBrF CF ₃ CF ₂ CH ₂ OH CF ₃ CH(OH)CH ₂ Br CF ₃ CH ₂ CH ₂ OH CF ₃ CH(OH)CH ₃ CH ₂ ClCH(OH)CH ₂ F CH ₂ FCH(OH)CH ₂ F CH ₂ FCH ₂ CH ₂ OH CH ₂ FCH(OH)CH ₃ CF ₃ (CF ₂ ) ₂ CH ₂ OH Perfluorocyclobutanol Perfluoro-tertiary butyl alcohol _CF3 ( _CF2 )C( _CH3 )OH C ₆ F ₅ CH ₂ OH (CF ₃ CF ₂ CF ₂ ) ₃ COH CF ₃ (CF ₂ ) ₈ CH ₂ OH CHF ₂ (CF ₂ ) ₁₃ CH ₂ OH CHF ₂ (CF ₂ ) ₁₅ CH ₂ OH CHF ₂ ( CF ₂ ) ₂₃ CH ₂ OH H (CF ₂ CF ₂ ) CH ₂ OH H (CF ₂ CF ₂ ) ₃ CH ₂ OH H (CF ₂ CF ₂ ) ₅ CH ₂ OH H (CF ₂ CF ₂ ) ₆ CH ₂ OH H(CF ₂ CF ₂ ) ₈ CH ₂ OH Substituted alcohol: (CF ₃ ) ₂ CFOCF ₂ CF ₂ (CF ₂ CF ₂ ) ₂ CH ₂ CHI
(CF ₂ ) ₉ OH (CF ₃ ) ₂ CFOCF ₂ CF ₂ (CF ₂ CF ₂ ) ₂ (CH ₂ ) ₁₁ OH Especially preferred as the fluorine-substituted organic radical of the terminal carboxylic acid ester group of the polyester of the present invention are: It is a fluorine-substituted organic radical corresponding to a primary fluorine-substituted saturated linear alcohol having the general formula H(CF ₂ CF ₂ ) _a CH ₂ OH (wherein a is an integer from 1 to 8). The above-mentioned fluorinated alcohols are covered by U.S. Patent No.
It is described in detail in the specification of No. 3036040,
The disclosure of which is incorporated herein by reference. The polyesters of the present invention generally have at least about Contains 5 to 100 mole percent fluorine-substituted aliphatic carboxylic acid ester end groups. Preferred polyesters of the present invention include about 25 to 100 mole percent, based on the total number of moles of end groups in the polyester;
In particular, it contains about 50 to 100 mole percent fluorine-substituted aliphatic carboxylic acid ester end groups. According to the process of the present invention, fluorine-substituted monofunctional alcohols containing from 1 to 45 carbon atoms, containing fluorine substituents corresponding to those desired for the fluorine-substituted carboxylate end groups of this polyester ) to form polyester. According to the production method of the present invention, the fluorine-substituted alcohol can be used simultaneously with or preferably prior to the polymerization esterification reaction of the diacyl halide and bisphenol. ) is reacted with. When the polyesters of the present invention are prepared by the reaction of fluorine-substituted alcohols of the type described above, the fluorine-substituted alcohols may be added at the end of, during, or during the polymerization esterification of the diacyl halide with the bisphenol reactant. is preferably added initially to the diacyl halide and reacted therewith. In other words, the fluorinated alcohol reactant of the present invention is reacted with the diacyl halide simultaneously with or subsequent to mixing the bisphenol and diacyl halide to initiate the polymerization reaction. In a preferred embodiment of the process of the invention, the fluoroalcohol is heated prior to contacting the diacyl halide reactant with the bisphenol, in particular under the same conditions as, for example, temperature, pressure, solvent and catalyst conditions used in the polymerization reaction. The mixture is then brought into contact with diacyl halide to substantially complete the esterification reaction. Preferred methods of making polyesters of the present invention provide for more complete reaction of the fluoroalcohol, ie, more complete conversion of the fluoroalcohol to the desired fluorine-substituted carboxylic ester end groups. A preferred method for preparing the polyesters of the present invention involves reacting a monofunctional hydroxyl reagent with a diacyl halide simultaneously with the polyesterification reaction between the diacyl halide and the bisphenol. ,
This differs from the prior art practice of reacting, for example, p-tertiary butylphenol. The fluorine-substituted aliphatic carboxylate group-terminated polyesters of the present invention may be prepared by the above-described modifications to known solution or interfacial processes for linear aromatic polyesters. In the polymerization esterification reaction of the diacyl halide of a dicarboxylic acid dissolved in a liquid that is a solvent for polyester produced in a general known interface method, the metal of bisphenol is dissolved in a liquid that is immiscible with the solvent for the diacyl halide. Condense with phenolate. The process for producing polyesters terminated with fluorocarboxylic acid ester groups according to the invention can be used in the production of known linear aromatic polyesters consisting of bisphenol and dicarboxylic acid monomer residues, in which diacyl halide reactants are used. and using essentially the same conditions (e.g., temperature and pressure), the same solvent and esterification catalyst, and the same polyester product recovery method. The above and known polyester manufacturing operations are described in U.S. Patent No.
Manufacturing method and PW disclosed in specification No. 3216970
“Conden Sation polymers” by Mergan
Interfacial and Solution Methods,
Interscience publishers, 1965, Chapter,
In particular, the polymerization methods described on pages 332-364 for the production of linear aromatic polyesters consisting of monomer residues of bisphenols and dicarboxylic acids are included. This U.S. Patent No. 3,216,970 and
The disclosure of Morgan's book is hereby incorporated by reference. Another known method for making linear aromatic polyesters is disclosed in the above-mentioned U.S. Pat. No. 3,471,441, the disclosure of which is incorporated herein by reference. is a homogeneous reaction of a difunctional aliphatic modifier, preferably a glycol having from 2 to about 100 carbon atoms, with a diacyl halide of a dicarboxylic acid, followed by an interface of the product with a bisphenol. It consists of polymerization.
The compositions produced by this process have monomeric residues of bisphenols and diacid halides and aliphatic modifiers such as glycols incorporated into the structure of the reaction product, resulting in high impact strength, high modulus, and improved It has excellent engineering properties such as good formability and high softening point. Such linear aromatic polyesters consisting of monomeric residues of bisphenols and dicarboxylic acids (including aliphatically modified polyesters of the type mentioned above)
Other known methods for producing
No. 4,051,106 and US Pat. No. 4,051,107, the disclosures of which are also incorporated herein by reference. The bisphenol compounds used in the reaction to produce the polyester of the present invention are known compounds and include bisphenols and bisphenols corresponding to the following general formula: where Ar is an aromatic group preferably containing 6 to 18 carbon atoms (including phenyl, biphenyl, and naphthyl); G is alkyl, aryl, alkylaryl, arylalkyl, or cycloalkyl; E is divalent (or disubstituted) alkylene,
alkylene, cycloalkylene or arylene,
-O-, -S-, -SO ₂ -, -SO ₂ -, -SO ₃ -, -
CO−,

[Formula] or GN<; T and T' are independently selected from the group consisting of G and OG; m
is an integer from 0 to the number of substitutable hydrogen atoms on E; b is an integer from 0 to the number of substitutable hydrogen atoms on Ar; x is 0 or 1; When there are multiple G substituents in the bisphenol, such substituents may be the same or different. T and
The T′ substituent is ortho with respect to the hydroxyl radical,
May occur in meta or para position. The hydrocarbon radicals mentioned above preferably have the following carbon atoms: 1-
Alkyl and alkylene with 14 carbon atoms;
Aryl and arylene with 6 to 14 carbon atoms; alkylaryl and arylalkyl with 7 to 14 carbon atoms; and cycloalkyl and cycloalkylene with 4 to 14 carbon atoms. Furthermore, mixtures of the above-mentioned suitable bisphenols can be used to obtain particularly desired properties. The bisphenols generally contain from 12 to about 30 carbon atoms, preferably from 12 to about 25 carbon atoms. Representative examples of bisphenols with the above general formula include bisphenol A [i.e., bis(4-hydroxyphenyl)-2,2-propane], bis(3-
hydroxyphenyl)-1,2-ethane, bis(4-hydroxyphenyl)-1,2-ethane, and those exemplified in column 2, line 68 to column 3, line 47 of U.S. Pat. No. 4,126,602. and other bisphenols, the subject matter of which is hereby incorporated by reference. Preferred bisphenols include P,P'-bisphenol and the aforementioned U.S. Pat. No. 4,126,602, column 3.
Other bisphenols exemplified in lines 47-55. Mixtures of the abovementioned bisphenols and bisphenol isomers may also be used. Preferably, the bisphenol monomer residues of the polyesters of the invention are derived from bisphenol-A. Aromatic dicarboxylic acids useful in the form of their corresponding diacyl halides in the preparation of the polyesters of the present invention are also known and are represented by the following general formula: In the formula, X is oxygen or sulfur, and Z is -Ar
- or -Ar-Y-Ar-, where Ar has the same definition as given for bisphenol and Y is alkylene of 1 to 10 carbon atoms, -O
−, −S−, −SO−, −SO ₂ −, −SO ₃ −, −CO−,

[Formula] or GN<, and n is 0 or 1. Suitable dicarboxylic acids include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid,
and column 4 of the above-mentioned U.S. Pat. No. 4,126,602;
Contains other aromatic dicarboxylic acids exemplified in lines 5 to 17. Preferably, the dicarboxylic acid monomer residues of the polyesters of the invention are derived from aromatic dicarboxylic acids, especially aromatic dicarboxylic acids selected from the group consisting of isophthalic acid, terphthalic acid and mixtures thereof. Preferably, the dicarboxylic acid component is about 75 to about
It consists of a mixture of 100 mole percent isophthalic acid and about 25 to about 0 mole percent terephthalic acid. If the dicarboxylic acid used to produce the polyester of the invention consists of both isophthalic acid and isophthalic acid according to a particularly preferred embodiment of the invention, the molar ratio of the residues of isophthalic acid and terephthalic acid in the polyester is about 75: A range of 25 to about 90:10 gives particularly satisfactory results. The difunctional aliphatic modifiers useful in preparing the aliphatic modified polyesters described in the aforementioned U.S. Pat. It is represented by the general formula: H _o D-A-D' _o H where D and D' are independently selected from the group consisting of O, S and N; A is a divalent or di-substituted aliphatic radical; without tertiary carbon, from alkylene, cycloalkylene, arylalkyl, alkyleneoxyalkyl, poly(alkylene-oxy)alkyl, alkylene-carboxyalkylene-carboxyalkyl, and poly(alkylene-carboxyalkylene-carboxy)alkyl n is an integer of 1 to 2, D and
If D' is N, n is 2. Typical examples of aliphatic modifiers having the above general formula are ethylene glycol and the above-mentioned U.S. Pat. No. 4,126,602, column 4, 55
Includes other difunctional modifiers exemplified in lines 66 to 66. Combinations of the above-mentioned difunctional aliphatic modifiers may also be used to generally achieve special properties. In the preparation of the polyesters of the present invention, the amount of fluoroalcohol used is generally about 0.1 molar amount of diacyl halide reactant used.
to about 50 mole percent or less. Preferably, relative to the number of moles of diacyl halide reactant,
Charge from about 0.1 to about 25 mole percent fluorinated alcohol. More preferably, the amount of fluoroalcohol used is from about 0.1 to about 10 mole percent, particularly from about 1 to about 5 mole percent, based on the moles of diacyl halide reactant. In preparing the polyesters of the present invention, the ratio of dicarboxylic acid diacyl halide and bisphenol reactant used provides at least some carboxylate group termination in the polyester product (i.e., the terminal residues of the polyester are (giving a polyester consisting of monomer residues of dicarboxylic acid reactants). As is known, carboxylate group termination in linear aromatic polyesters consisting of monomer residues of bisphenols and dicarboxylic acids (rather than bisphenols and any difunctional aliphatic modifier reactants used) A stoichiometric excess of dicarboxylic acid reactant to a slight stoichiometric deficit corresponding to approximately 5 mole percent stoichiometric excess of bisphenol and all difunctional aliphatic modifier reactants. This results in the use of molar ratios of the dicarboxylic acid reactants that range from the dicarboxylic acid reactants. Preferably, the polyesters of the present invention are prepared using a molar amount of dicarboxylic acid reactant that is approximately stoichiometrically equivalent to the molar amounts of bisphenol and any difunctional aliphatic modifier reactants used. . The fluorinated alcohols of this invention act as molecular weight control agents for the polyester products of this invention. Therefore, as the molar ratio of fluorinated alcohol to the number of moles of diacyl halide reactant charged to the polyester production process increases, the molecular weight of the product polyester decreases. That is, when a high proportion of fluorine-substituted alcohol is used in the production of the polyester of the present invention, a polyester with a low molecular weight is obtained. The high molecular weight polyesters of the invention described above, which are generally obtained using about 25 mole percent or less of fluoroalcohol (based on moles of diacyl halide reactant), have a degree of polymerization (dp) of 8 or greater (d.p. of 8 or greater).
p. corresponds to the presence of 7 bisphenol monomer residues and 8 dicarboxylic acid monomer residues in the polyester), characterized by a degree of polymerization of, for example, 35 to 50 or even more. . In general, the above-mentioned low molecular weight polyesters obtained by the use of 25 mole % or more of fluoroalcohol (relative to the number of moles of diacyl halide reactant) are characterized by a degree of polymerization of 8 or less, for example 3. The polyester products of the present invention exhibit increased hydrolytic stability (with respect to retention of tensile strength) compared to corresponding conventional linear aromatic polyesters having approximately the same molecular weight and consisting of bisphenol-dicarboxylic acid monomer residues. while retaining almost all of the beneficial physical and chemical properties of these known polyesters. The above-mentioned beneficial effects of the present invention are due to the fact that, together with the fluorine-substituted ester end groups of the present invention, other carboxylic acid ester end groups (such as esters derived from monofunctional phenols and aliphatic hydrocarbon monofunctional ayucols) are present in the polyesters. is achieved even in the presence of The above-mentioned low molecular weight polyesters of the present invention obtained using a high molar ratio of fluorinated alcohol reactants also exhibit increased stability against hydrolysis;
It is useful as an additive to conventional linear aromatic polyesters consisting of bisphenol and dicarboxylic acid monomer residues, thereby increasing the water resistance of the conventional polyesters. The polyesters of the present invention can be easily formulated with additives with various functions, such as organic or inorganic fillers (eg glass fibers), stabilizers, antistatic agents and flame retardants. As a flame retardant December 22, 1977
The halogen-containing additives disclosed in US Patent Application Nos. 863,556 and 863,381 are particularly suitable for the polyesters of the present invention. The disclosures of these applications are hereby incorporated by reference. The polyesters of this invention are readily processed in conventional injection and extrusion equipment into molded articles such as miniature circuit boards for electrical equipment. The following examples further illustrate various aspects of the invention, but are not intended to limit it. Various changes may be made to the invention without departing from the spirit and scope of the invention. In this specification and claims, unless otherwise indicated, temperatures are expressed in degrees Celsius and all parts and percentages are given by weight. Example 1 Isophthaloyl chloride (228.4 g, 1.125 mol), terephthaloyl chloride (76.1 g, 0.375 mol), EIDu Pont de Nemours
Fluoro-alkyl alcohol of general formula H(CF ₂ CF ₂ ) ₅ -CF ₂ OH (19.1 g, 0.0359 mol,
corresponding to about 2.4 mol % based on the moles of isophthaloyl and terephthaloyl chloride, and containing about 71% fluorine), and the distilled methylene chloride of 3,
Charge a Morton flask equipped with an addition funnel, nitrogen inlet, mechanical stirrer, thermometer and condenser. Distilled triethylamine esterification catalyst (3.6 g, 0.0359 mol) was charged to the reaction vessel;
The resulting mixture is stirred for about 16 hours to complete the reaction between the fluorinated alcohol and the diacyl halide reactant. Therefore, bisphenol A (338.5 g, 1.482 mol,
containing only 0.025% water), isophthaloyl and terephthaloyl chloride, and its -COCl
Some of the chloride substituents of the substituents are introduced into the reaction mixture which has already been substituted (ie esterified with the fluoro-alkyl group) with the fluoro-alkyl group of the fluorine-substituted aliphatic alcohol. Replenishment of triethylamine catalyst (309.0g, 3.054mol)
is gradually added to the reaction mixture over a period of 1.75 hours, during which time the reaction mixture is stirred at about 20-23°C. After this catalyst addition is complete, the reaction mixture is substantially
The mixture was further stirred for 2 hours under the above temperature conditions to complete the polyesterification reaction. The resulting white, translucent, viscous polymer mass is transferred to a separate container and about 900 ml of distilled water containing 12 ml of concentrated hydrochloric acid are added to the mixture while stirring. The mixture is then separated into an aqueous layer and an organic layer. Collect the organic layer,
Wash with distilled water until chloride ions are removed. The resulting washed polymer solution is passed through a sintered glass filter in the presence of 50 g of supercharging agent to obtain a clear pale yellow liquid. The polymer product is precipitated by slowly adding isopropyl alcohol to the filtered polymer solution while stirring (using an equal volume of isopropyl alcohol to the solution). Most of the methylene chloride is distilled off from the polymer solution during the isopropyl alcohol addition. The white solid polymer product recovered by filtration is air dried at ambient temperature for about 16 hours and then dried in an open vacuum at 100° C. for several hours to remove residual methylene chloride. The molar ratio of isophthalic acid monomer residues to terephthalic acid monomer residues is approximately 75:25, and approximately 50 mole percent of the carboxylic acid ester end groups (all end groups in the polyester) are derived from the polyfluoroaliphatic alcohol reactant. Approximately 454 g of bisphenol A-isophthalate-terephthalate polyester with hydroxyl and carboxylate end groups) is obtained. This polyester product has an intrinsic viscosity of about 0.57 dl/g measured as a 0% polyester product solution in symmetrical tetrachloroethane at 30°C. The weight average molecular weight and number average molecular weight of this product are 33100 and 13400, respectively.
The degree of polymerization (dp) of this product is approximately 35. The polyester product is dried at 120° C. for 2 hours and melt extruded in a Haake extruder under the following conditions:

Table: The product is extruded as a clear resin with a very pale yellow tinge. The extruded product strand is cooled to ambient temperature and cut into granules. It has an intrinsic viscosity of 0.57 dl/g, measured as described above. The granules are dried and injection molded in an Arburg injection molding machine operated under the following conditions: Cylinder temperature: Zone 1 640〓 (337.8°C) Zone 2 640〓 (337.8°C) Mold temperature 250〓 (121.1° C.) Screw speed 240 rpm Injection pressure 19980 psi (1398.6 Kg/cm ² ) Plasticization time 8 seconds The intrinsic viscosity of this injection molded product is 0.54 dl/g as measured as described above. The hydrolytic stability of this injection molded product was tested by measuring its tensile strength and tensile modulus before and after immersing it in boiling water for 7 days. The test results are shown below. Example 2 (Control) Bisphenol A (21657 g, 94.835 mol), isophthaloyl chloride (14617 g, 72 mol), terephthaloyl chloride (4873 g, 24 mol), p-tert-butylphenol (polyester chain terminator, (350 g, 233 moles, equivalent to 2.4 mole percent based on the moles of isophthaloyl and terephthaloyl chloride) and 500 pounds (226.8 Kg) of dry methylene chloride in a dry 100 gallon (378) reactor under a dry nitrogen atmosphere. Charge to. Triethylamine catalyst (197.76 moles) is charged under nitrogen flow to a 50 gallon (189) dry addition vessel connected to the 100 gallon reactor described above. Over a period of 2 hours and 22 minutes, this catalyst is added at a constant rate to the reaction mixture in a 100 gallon reactor that is maintained at 20-24°C and stirred. After the catalyst addition is complete, the reaction mixture is stirred for 3 hours at 18-20°C to complete the polymerization. The product is collected and dried as described in Example 1.
This product, with an intrinsic viscosity of 0.64 dl/g (measured as in Example 1), has a molecular weight approximately equal to that of the product of Example 1, with a ratio of approximately 75:25 isophthalic acid monomer residues: terephthalic acid monomer residues. It is a bisphenol A-isophthalate-terephthalate polyester having a molar ratio of . This product contains p-tertiary butylphenyl carboxylic ester substituents (approximately 50 of the total polyester end groups) as carboxylate end groups on the polyester in place of the fluoro-alkyl carboxylic ester end groups of the product of Example 1. Structurally comparable to the product of Example 1 except that mol %) is present. This product is processed at the Farrell Mill.
(front roll temperature of 450〓 [232.2℃], 425〓
Compacted by kneading under melt conditions for 2.5 to 30 minutes in a [218.3°C] downstream roll temperature (operating at a roll speed of 45 rpm) and then New Britain 75 injection under the following operating conditions: Injection mold in molding equipment substantially according to the procedure of Example 1: Cylinder temperature: Zone 1 630〓 [332.2°C] Zone 2 610〓 [321.1°C] Molding temperature 239〓 [115°C] Screw speed 76 rpm Injection pressure 20000 psi [1400 Kg/cm ² ] Plasticization time 10 seconds This injection molded product with an intrinsic viscosity of 0.53 dl/g (determined as described above) is tested for stability against hydrolysis as in Example 1. The results of this test are compared with the results of the product of Example 1 in the table below. Example 3 (control) having a p-tertiary butyl phenyl carboxylic acid ester group end and having a molar ratio of isophthalic acid monomer residues to terephthalic acid monomer residues of about 85: instead of 75:25 (Example 2). A bisphenol A-isophthalate-terephthalate polyester having substantially the same structure as the product of Example 2, except that 15, is prepared and molded in much the same manner as in Example 2. The stability of the product against hydrolysis is evaluated by measuring the tensile strength of the product before and after immersion of the molded product in boiling water for 7 days (as in Example 2). The results of this test are also reported in the table below.

[Table] The data in the above table shows that the fluoro-alkyloxycarbonyl-terminated, i.e., fluoro-alkyl ester group-terminated linear aromatic polyester of the present invention has a tensile strength of only about 10% of its initial tensile strength when immersed in boiling water for 7 days.
This shows that the loss is only 18.4%. In contrast, the corresponding polyesters substituted with p-tert-butylphenoxycarbonyl end groups (as carboxylate end groups) in the controls of Examples 2 and 3 exhibited an initial tensile strength after 1 week immersion in boiling water. Loss of strength ranges from about 71% or more to about 80% or more. Therefore, the above data is based on this fluoro-
The alkyl ester-terminated polyester is significantly more stable to hydrolysis than the p-tertiary butyl phenyl ester-terminated polyesters of Examples 2 and 3 (with respect to retention of tensile strength). Illustrated. p-tertiary butyl phenyl ester-terminated bisphenol-isophthalate-terephthalate polyesters have been shown to be more stable to hydrolysis than corresponding polyesters without carboxylic acid ester end groups (the characteristics mentioned above). The results of this data comparison described above also show that the fluoro-alkyl ester-terminated polyesters of the present invention are more susceptible to hydrolysis than the corresponding polyesters lacking carboxylic acid ester end groups. It shows that it is stable. Note that a polyester product prepared in the same manner using stearyl alcohol in place of the fluoroalkyl alcohol used in Example 1 (approximately
Polyester substantially similar to Example 1 except containing 50 mole % stearate ester end groups)
The loss in tensile strength after 7 days of boiling water immersion is approximately
It was 32%. Although this is less loss in tensile strength than the approximately 71-80% loss of p-tertiary butyl phenyl ester terminated polyester, it is a greater loss than the inventive polyester of Example 1. Example 4 The process described in Example 1 is repeated in substantially the same manner, except that the fluorinated alcohol of Example 1 is added to the polymerization reaction mixture simultaneously with the bisphenol A reactant and the diacyl halide reactant. A bisphenol-isophthalate-terephthalate polyester product containing a fluoro-alkyloxycarbonyl terminal ester substituent is obtained, which exhibits increased resistance to hydrolysis (with respect to retention of tensile strength), as shown in Example 1 The resistance to hydrolysis is virtually identical to that of the polyester products. Example 5 The procedure of Example 1 is repeated in substantially the same manner, except that the fluorine-substituted monofunctional alcohol used is H(CF ₂ CF ₂ ) ₈ CH ₂ OH. General formula - COOCH ₂
A bisphenol-isophthalate-terephthalate polyester with (CF ₂ CF ₂ ) ₈ H ester end groups is obtained as product. This product has excellent properties. Example 6 The procedure of Example 1 is repeated in substantially the same manner, except that the fluorine-substituted monofunctional alcohol is used as H(CF ₂ CF ₂ ) ₃ CH ₂ OH. As a product, the general formula −
A bisphenol-isophthalate-terephthalate polyester with COOCH ₂ (CF ₂ CF ₂ ) ₃ H ester end groups is obtained. This product has excellent properties. Example 7 The fluorine-substituted monofunctional alcohol used is
Substantially the same procedure as Example 1 is repeated, except that HCF ₂ CF ₂ CH ₂ OH. As a product, the general formula −
A bisphenol-isophthalate-terephthalate polyester with ester end groups of COOCH ₂ CF ₂ C ₂ H is obtained. This product has excellent properties. The invention has been described above and illustrated with reference to specific embodiments in illustrative examples. however,
It is understood that these embodiments are illustrative and are not intended to limit the invention, as changes and modifications may be made without departing from the scope and spirit of the invention. Should.

Claims (1)

[Claims] 1. A linear aromatic polyester consisting of a monomer residue of a bisphenol compound and an aromatic dicarboxylic acid, in which the terminal residue of the polyester chain is the dicarboxylic acid residue, and the degree of polymerization is 2 or more. , from a fluorine-substituted saturated aliphatic monofunctional alcohol whose terminal dicarboxylic acid residue has the general formula H(CF ₂ -CF ₂ ) _a CH ₂ OH (wherein a is an integer from 1 to 8) characterized in that the proportion of the ester substituent derived from the fluorine-substituted aliphatic alcohol is at least 5 mol % based on the total number of moles of terminal groups in the polyester. Linear aromatic polyester. 2 The aromatic dicarboxylic acid has the general formula (However, in the formula, Z is -Ar- or -Ar-Y-Ar-
and this Ar is an aromatic group, and Y is alkylene, haloalkylene, -O-, -S-, -SO ₂ -,
-SO ₃ -, -CO-, [Formula] or GN<, and this G is alkyl, haloalkyl, aryl, haloaryl, alkylaryl, haloalkylaryl, arylalkyl, haloarylalkyl, cycloalkyl, or cyclohaloalkyl. , and n is 0 or 1). 3 The aromatic dicarboxylic acid is isophthalic acid,
A polyester according to claim 2 selected from the group consisting of terephthalic acid and mixtures thereof. 4 The bisphenol compound has the general formula (However, in the formula, Ar is an aromatic group, and G is alkyl, haloalkyl, aryl, haloaryl, alkylaryl, haloalkylaryl,
arylalkyl, haloarylalkyl, cycloalkyl, or cyclohaloalkyl; E
is divalent alkylene, haloalkylene, cycloalkylene, halocycloalkylene, arylene, or haloarylene, -O-, -S-, -SO-, -
SO ₂ -, -SO ₃ -, -CO-, [Formula] or GN <; T and T' are independently selected from the group consisting of halogen, G and OG; m is from 0 to the substitution on E; b is an integer from 0 to the number of replaceable hydrogen atoms on Ar; x is 0 or 1), The polyester according to any one of items 1 to 3. 5. The polyester according to claim 4, wherein the bisphenol compound is bisphenol-A. 6. The polyester of any one of claims 1 to 5, wherein about 25 to about 100 mole percent of the polyester end groups are carboxylic acid ester groups derived from the fluorine-substituted primary alcohol. . 7. The polyester of claim 6, wherein from about 50 to about 100 mole percent of the polyester end groups are carboxylic acid ester groups derived from said fluorine-substituted primary alcohol. 8. The polyester according to any one of claims 1 to 7, wherein a is 5. 9 A method for producing a linear aromatic polyester consisting of monomer residues of a bisphenol compound and an aromatic dicarboxylic acid by a polymerization esterification reaction of the bisphenol compound and a diacyl halide of the dicarboxylic acid, the method comprising: Up to 25 mol%, based on the number of moles of halide, of a fluorine-substituted saturated monofunctional compound having the general formula H(CF ₂ -CF ₂ ) _a CH ₂ OH, where a is an integer from 1 to 8. By reacting an aliphatic alcohol and introducing it into the polyester, the proportion of ester substituents derived from the fluorine-substituted aliphatic alcohol is at least 5 mol % with respect to the total number of moles of terminal groups in the polyester. A method for producing a linear aromatic polyester, characterized in that: 10 The fluorine-substituted alcohol is reacted with the diacyl halide reactant prior to the polymerization esterification reaction of the diacyl halide and bisphenol, and the molar ratio of the fluorine-substituted alcohol is
10. The method of claim 9, wherein the amount is from 0.1 to 25 mol%. 11 The fluorine-substituted alcohol is mixed with the diacyl halide at the same time as bisphenol and diacyl halide are mixed, and reacted to initiate the polymerization esterification reaction, and the molar ratio of the fluorine-substituted alcohol is 0.1 to 25. 10. The method of claim 9, wherein the amount is mol %. 12 The aromatic dicarboxylic acid has the general formula (However, in the formula, Z is -Ar- or -Ar-Y-Ar-
and this Ar is an aromatic group, and Y is alkylene, haloalkylene, -O-, -S-, -SO ₂ -,
-SO ₃ -, -CO-, [Formula] or GN<, and this G is alkyl, haloalkyl, aryl, haloaryl, alkylaryl, haloalkylaryl, arylalkyl, haloarylalkyl, cycloalkyl, or cyclohaloalkyl. , and n is 0 or 1).
The method described in any of Item 1. 13. The method of claim 12, wherein the aromatic dicarboxylic acid is selected from the group consisting of isophthalic acid, terephthalic acid, and mixtures thereof. 14 The bisphenol compound has the general formula (However, in the formula, Ar is an aromatic group, and G is alkyl, haloalkyl, aryl, haloaryl, alkylaryl, haloalkylaryl,
arylalkyl, haloarylalkyl, cycloalkyl, or cyclohaloalkyl; E
is divalent alkylene, haloalkylene, cycloalkylene, halocycloalkylene, arylene, or haloarylene, -O-, -S-, -SO-, -
SO ₂ -, -SO ₃ -, -CO-, [Formula] or GN <; T and T' are independently selected from the group consisting of halogen, G and OG; m is from 0 to the substitution on E; b is an integer from 0 to the number of replaceable hydrogen atoms on Ar; x is 0 or 1), The method according to any one of Items 9 to 13. 15. The method of claim 14, wherein the bisphenol compound is bisphenol-A. 16. The method according to any one of claims 9 to 15, wherein a is 5.